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The Thermodynamics of Technetium and Its Compounds University of Tennessee, Knoxville TRACE: Tennessee Research and Creative Exchange Doctoral Dissertations Graduate School 6-1952 The Thermodynamics of Technetium and Its Compounds James W. Cobble University of Tennessee, Knoxville Follow this and additional works at: https://trace.tennessee.edu/utk_graddiss Part of the Chemistry Commons Recommended Citation Cobble, James W., "The Thermodynamics of Technetium and Its Compounds. " PhD diss., University of Tennessee, 1952. https://trace.tennessee.edu/utk_graddiss/4376 This Dissertation is brought to you for free and open access by the Graduate School at TRACE: Tennessee Research and Creative Exchange. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of TRACE: Tennessee Research and Creative Exchange. For more information, please contact [email protected]. To the Graduate Council: I am submitting herewith a dissertation written by James W. Cobble entitled "The Thermodynamics of Technetium and Its Compounds." I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the equirr ements for the degree of Doctor of Philosophy, with a major in Chemistry. William T. Smith, Jr., Major Professor We have read this dissertation and recommend its acceptance: Hilton A. Smith, Seymour Bernstein, G. E. Boyd Accepted for the Council: Carolyn R. Hodges Vice Provost and Dean of the Graduate School (Original signatures are on file with official studentecor r ds.) May 26, 1952 To the Graduate Council: I am submitting to you a dissertation written by James w.1 Cobble entitled "The Thermodynamics of Technetium and Its Compounds. 1 I recommend that it be accepted in partial fulfillment of the require­ ments for the degree of Doctor of Philosophy, with a major in Chemistry. We have read this dissertation and recommend its acceptance: Accepted for the Council ,, THE THERMODYNAMICS OF TECHNErIUM AND ITS COMPOUNDS A DISSERTATION Submitted to The Graduate Council of The University of Tennessee in Partial Fulfillment of the Requ:irerents for the Degree of Doctor of Philosophy by James W. Cobble June, 19.52 ,I ACKNOWLEDGEMENI' The author wishes to express his appreciation to the Graduate School of the University of Tennessee, the Oak Ridge Institute of Nuclear Studies, and the Chemistry Division, Oak Ridge National Labora­ tory for their cooperation :in mak:ing possible the carrying out of this research through the Oak Ridge Resident Program. His deepest appreciation is expressed to Professor w. T. Smith, Jr., and Dr. G. E. Boyd, without whose earnest encouragement and guidance this dissertation would not have been possible. To Margaret Ann TABLE OF CONTENTS CHAPI'ER PAGE Io INTRODUCTIONo • 00000000• . 1 II. PREPARATION AND IDENTIFICATION OF COMPOUNDS •. 4 Ao Preparation of Technetium Metal o o o • 4 Bo Preparation of Technetium Heptoxide .. 7 C. Preparation of Pertechnic Acid o 9 D. Ammonium Pertechnetate •. ••• • 0 • • • • • • 9 E. Preparation of Technetium Dioxide • ••12 F. Technetium Trioxide ••••• . 17 G. Other Compounds of Technetium • . • • 19 III. VAPOR PRESSURE STUDIES•••••• • • 21 A. The Vapor Pressure of Technetium Heptoxide••••• 21 B. The Vapor Pressure of Pertechnic Acid •• 32 c. The Vapor Pressure over Saturated Pertechnic Acid • • 35 IV• CALORIMETRY 0 0 0 0 . 0 . 0 . 39 A. The Heat of Combustion of Technetium Metal. 39 Bo The Heat of Solution of Technetium Hepto xide. 53 c. The Heat of Dilution of a Pertechnic Acid Solution. 0 . 0 . 0 . 56 v. OXIDATION REDUCTION CELLS 0 0 0 0 . 61 A. Acid Cell •• 0 0 0 000000000 62 B� Basic Cell. • 0 • • • • • • • • 67 V C!fAPTER PAGE VI. THERMOCHEMICAL CALCULATIONS • • • •• · ••. 72 A. The Free Energies, Heats and Entropies of Formation of Technetium (VII) Compounds. 72 Bo The Free Energy, Heat and Entropy of Form9.tion of Technetium Dioxide . 78 c. The Free Energy, Heat and Entropy of Formation of Technetium Trioxide. 79 D. The Oxidation-Reduction Scheme for Technetium . 0 . • • 0 . 82 E. Comparison of the Properties of Sub- Group VII 0 . 82 VII. SUMMARY . 94 APPENDIXES. e>o••oo•••• . 96 I. X-RAY DIFFRACTION POWDER PATTERNS 97 II. PHYSICAL CONSTANTS, , .••••• 103 III. TREATMENI' OF THE CALORIMETRIC DATA. 105 IV. THE HEATS OF COMBUSTION OF RHENIUM AND RHENIUM TRIOXIDE•••••••• •••••••• 108 V. ESTIMATION OF ENTROPY VALUES FOR TECHNEI'IUM AND ITS COMPOUNDS. ll5 ., BIBLIOGRAPHY • • • • • • • • o o • o • • • • • 122 LIST OF TABLES TABLE PAGE I. Weight Loss Study on the Hydrogen Reduction of Ammonium Pertechnetate ••• . 6 II. Analysis of Technetium Dioxides • • . 15 III. Summary of Known Technetium Compounds • 0 0 0 0 • • • • 20 IV. The Vapor Pressure of Solid Technetium Heptoxide • . • . • • • • • . • • • • • 0 • • • • • • 27 V. The Vapor Pressure of Liquid Technetium Heptoxide . • o • • • • • • • • • • • • • • • • 28 VI. Comparison of Thermodynamic Properties of Technetium and Rhenium Heptoxides .••• . .•31 VII. The Dissociation Pressure· of Pertechnic Acid. · • • 33 VIII. The Vapor Pressure of Water ov er Saturated Pertechnic Acid Solutions •••••••••••••••37 IX. Thermodynamic Data for Salvation Reactions of Technetium and Rhenium Heptoxides •••••••• • 38 x. Heat of Combustion of Paraffin Oil Accelerator •• • 46 XI. Benzoic Acid Combustion Calibration •• • • 48 XII. Heat of Combustion of Technetium Metal •• • • 50 XIII. Calibration of Solution Calorimeter •• . • • • 57 XIV. Heat of Solution of Technetium Heptoxide. • 58 xv. EMF of the Technetium Dioxide-Pertechnetate Electrode in Pertechnic Acid Solutions •••••••••65 vii TABLE PAGE XVI. EMF of the Technetium Diox:ide-Pertechnetate Electrode in Basic Solution •• .•••••••••• 70 XVII. The Heat of Formation of Potassium Pertechnetate o ••• 0 • 0 0 0 e e 77 XVIII. Summary of Thermodynamic Properties of Technetium and Its Compounds .•••• . • 0 • • 83 XIX. Comparison of Properties of Sub-Group VII . • • 87 XX. Comparison of X-ray Diffraction Patterns for Technetium and Rhenium Heptoxides • • • • • • 98 XXI. Comparison of Technetium Metal X-ray Patterns••• . · · · · · · · • 99 XXII. Interplanar Distances for Technetium Dioxide Prepared by Pyrolysis of Ammonium Pertechnetate •••• . 101 XXIII. Physical Constants•• . 104 XXIV. Heat of Combustion of Rhenium Metal • • 110 xxv. The Heat of Combustion of Rhenium Trioxide•• • 112 XXVI. Summary of Entropies Estimated fo r Technetium and Some of Its Compounds •. • •••••.•••••121 LIST OF FIGURES FIGURE PAGE 1. Potentiometric Titration of a 0.1 M. Pertechnic Acid Solution. • • • • • • • • • • • . • • 0 • 10 2. Beer's Law Plot for Aqueous Ammonium Per- technetate Solutions . • • • 0 13 J. Sickle Gauge • . • . 22 4. Sickle Gauge (Photograph) . • . 23 5. Vapor Pressure Apparatus . 26 6. Vapor Pressure of Technetium Heptoxide . 30 7. Vapor Pressure of H20 over HTc04(s) and IITc04(sat.)· • 34 8. Combustion Calorineter •• . 40 9. Combustion Calorimeter • 41 10. Micro-Combustion Bomb •. 43 ll. Solution Calorimeter .. • • 54 12. Oxidation-Reduction Diagram for Technetium •. • . 85 lJ. Oxidation-Reduction Diagram for Sub-Group VII. 91 14. X-ray Powder Pattern for Technetium Dioxide..••• . 102 15. Time-Temperature Curve for Calorimeter •••. • 106 CHAPTER I INTRODUCTION The recent1 large scale separation of technetium from the uranium fission products at the Oak Ridge National Laboratory .has made possible an investigation of the chemistry of technetium-using much larger quantities than have previously been availableo Although 2 element 43 was reported by the Noddacks in 1925 , they have not pub­ lished any further information on the element. In 19353 Perrier and SegrJ bombarded molybdenum in a cyclotron with energetic deuteron particles and produced an isotope whose chemistry followed that expected for element 4Jo Because of the criticism of the Noddacks' 4 evidence of element 43 , ani the further fruitless attempts of others to repeat their work.5, 6, it now seems well established that the first bona fide chemical evidence for element 43 was that of Perrier and Segre. The International Union of' Chemistry has accepted their claim and the name which they gave to it, technetium. ? 11 (1) Performed by the Ho�' Laboratory Group, Chemistry Division, Oak Ridge National Laboratory. (2) Noddack, w., Tacke, I., and Berg, o., Naturwissenschaften, 13, 567 (1925). I (3) Perrier, c. and Segre, E., !!.:_Chem. Phys.,�' 712 (1937); ibid., 1, 155 (1939). (4) Prandtl, w., � angew. Chem., 39, 1049 (1926). (5) Prandtl, w., Ber., 60, 621 (1927). (6) von Hevesy, G., Chem. Rev., J, 321 (1927). (7) Committee on New Elements, International Union of Chemistry, Chem. Engo News, 27, 2996 (1939). 2 Until the occurrence of the chain reacting pile, only unweigh­ able quantities had been produced by cyclotron bombardments of molyb­ denum; much of the previous 11 tracer11 chemistry has been summarized recently by Hackneyo8 Since the War fractional milligram quantities9 have been produced by prolonged neutron irradiation of molybdenum in the Oak Ridge National Laboratory graphite reactor o Milligram quan­ titites were also isolated10 from fission product solutions from project sources in 1948. In the sunnner of 1951, fractional gram quantities became available for research purposes.11 It was felt that a thermodynamic study of -�he element and its compounds would be of primary interest in help:ing complete the thermo­ dynamic data available on the transition elements. Such data are of aid :in �derstanding the role of the d electrons in chemical bonding. In addition, the chemical similarities and
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